One of the major technological challenges that currently exist worldwide in naturally fractured carbonate reservoirs (NFCR) than they present high temperature and high salinity conditions; it is to increase the oil recovery factor through the use of chemicals. The NFCR are characterized by possessing low porosities, present areas of preferential flow, this due to the existence of fractures and dissolution cavities and exhibit wettability to the oil or intermediate; therefore, chemicals that are used in the same, in order to increase the recovery factor, must be possess the ability to control the channeling of fluid and alter the rock wettability of oil-wet to water-wet. Added to this, if in the NFCR conditions of high temperature and salinity, and problems of incompatibility between the injection water and formation water, it is necessary that the chemicals that are used in enhanced oil recovery processes, be tolerant to high salinity and concentrations of divalent ions, control problems of formation damage caused by mineral salt scale and problems of uniform corrosion as well as scales in the production rigs.
Traditionally, the way to control channeling of fluids in NFCR has been through the use of foaming agents and/or gels [SPE 145718, 2011, Development of a new foam EOR model from laboratory and field data of the naturally fractured Cantarell Field; SPE 130655, 2010, High-temperature conformance field application through coiled tubing a successful case history; SPE 129840, 2010, Application of gas for mobility control in chemical EOR in problematic carbonate reservoirs and the performance thereof, is a function of reservoir temperature, salinity and concentration of divalent ions that are present in water injection and/or in the formation water and the type of crude oil which are present in the reservoir. Also, the benefits of use foaming agents with wettability modifying properties that control gas channeling problems and increase the recovery factor in NFCR that not present incompatibility of waters problems has been recently demonstrated in Mexico [AIPM, 13-33, 2012, Control de movilidad del gas en el casquete en pozos del campo Akal perteneciente al Complejo Cantarell; SPE 145718, 2011, Development of a new foam EOR model from laboratory and field data of the naturally fractured Cantarell Field]. Additionally, the foaming agents are commonly used in various stages of the exploitation of oil fields as: drilling and fracturing; as well as in gas reservoirs and condensates with water supply. In this type of gas and condensate reservoirs, the function of the foam is to maximize the gas production through the weight reduction of the hydrostatic column generated by fluids (water, gas and condensate). Within the main chemical families of surfactants that have been used to generate foams and which have application in enhanced oil recovery processes are: 1) Alkyl aryl sulfonates (U.S. Pat. No. 5,273,682 “Viscosity control additives for foaming mixture”); 2) Alkoxy alkyl benzenesulfonates (U.S. Pat. No. 5,049,311 “Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications”); 3) Alpha olefin sulfonate (U.S. Pat. No. 4,607,695 “High sweep efficiency steam drive oil recovery method”); 4) Alkyl amido betaines (U.S. Pat. No. 7,104,327 “Methods of fracturing high temperature subterranean zones and foamed fracturing fluids therefor”); 5) Alkyl amido hydroxysultaines (U.S. Pat. No. 7,407,916 “Foamed treatment fluids and associated methods”); and 6) Alkyl ether sulfates (Report DE-FC26-03NT15406 of the United States Department of Energy in America Surfactant-Based Enhanced Oil Recovery Processes and Foam Mobility Control). However, when in the reservoirs, the temperature conditions are high (higher than 70° C.), the salinity is greater than 30,000 ppm of total solids and the concentration of divalent ions, such as, calcium and magnesium, it is more than 2,000 ppm, so that, the stability of the foam that are generated for this kind of chemicals families of surfactants decreases drastically. In order to increase the stability of the foam and thus its tolerance to high concentrations of divalent ions and/or temperature, they have been developed formulations of foaming agents with improved properties as those listed below: The U.S. Pat. No. 3,939,911 (Surfactant oil recovery process usable in high temperature formations containing water having high concentrations of polyvalent ions) describes a system of three surfactants applied to processes of enhanced recovery in reservoirs of high temperature and whose water formation contains of 200 to 14,000 ppm of polyvalent ions dissolved, such as calcium or magnesium. The system of three surfactants is made up of: 1) a water-soluble salt of an alkyl or alkylaryl sulfonate, wherein the alkyl chain can be have from 5 to 25 carbon atoms, 2) a surfactant of phosphate ester with an average molecular weight which does not exceed 1000 UMA and 3) a sulfobetaine surfactant of the structural formula (1) wherein R is an alkyl group of 12 to 24 carbon atoms. The combination is stable until at least a temperature of 107° C. and resistant to attack by bacteria and inhibits scale formation.

The U.S. Pat. No. 4,703,797 (Sweep improvement in enhanced oil recovery) mentions a method of improved swept during processes of enhanced oil recovery. The method consists of generate a foam by the dispersion of the fluid displaced in an aqueous solution containing a surfactant formulation. The surfactant formulation consists of a foaming based lignosulfonates and a foaming surfactant. Within the foaming surfactants mention is made to the group consisting of anionic, nonionic and amphoteric surfactants. The U.S. Pat. No. 5,295,540 (Foam mixture for steam and carbon dioxide drive oil recovery method) mentions a method based foams for the enhance the hydrocarbons production in subterranean formations and consisting of: 1) inject vapor and fluids produced into the formation and 2) injecting a vapor mixture, a non-condensable gas and an aqueous mixture of surfactant and polysaccharide. Within the surfactants mentioned which can be used, they are find linear toluene sulfonates, alkylaryl sulfonates, dialkylaryl sulfonates, alpha olefin sulfonates and dimerized alpha olefin sulfonates. The U.S. Pat. No. 5,542,474 (Foam mixture for carbon dioxide drive oil recovery method) mentions a method based foam to enhance the performance during the steam supply or carbon dioxide into underground formations that containing crude oil and which are formed by at least one producer well and one injector well. The sweep efficiency in the oil recovery process through steam supply is enhanced by: 1) inject steam until it starts to appear in the producer well and 2) then add to the forming a mixture of steam, not condensable gas and an aqueous solution of a polypeptide surfactant. The aqueous solution of surfactant-polypeptide forms a stable foam with the oil of the formation at reservoir conditions. Within the surfactants used as base of foaming agent are sodium salts and ammonium of sulfated ethoxylated alcohols, ethoxylated linear alcohols, linear toluene sulfonates. The U.S. Pat. No. 7,104,327 (Methods of fracturing high temperature subterranean zones and foamed fracturing fluids therefor) provides methods for fracturing subterranean zones of high temperature and aqueous fracturing fluids foamed and viscous for this purpose. The fracturing fluid of the invention take in water, a terpolymer of 2-acrylamido-2-methylpropane sulfonic acid, acrylamide and acrylic acid or salts thereof, a gas, a foaming agent and a breaker of viscosity for controlling and reduce the viscosity of the fracturing fluid. The foaming agent in this invention is selected from the group consisting of C8-C22 alkylamido-betaine, alpha olefin sulfonate, chloride of trimethyl-taloil-ammonium C8-C22 alquiletoxilado sulfate and chloride of trimethyl-coco-ammonium; especially mention is made as foaming agent of the cocoamidopropyl betaine. The Mexican patent MX 297,297 (Composición espumante para alta temperatura y salinidad) is related to a foaming composition with enhanced that control the gas channeling in carbonate naturally-fractured reservoirs with high-salinity and temperature conditions through the synergistic effect resulting from the supramolecular interaction of alpha olefin sulfonates of sodium with alkyl amido propyl betaines [structure (2)],
wherein R and R1 are independent alkyl chains linear or branched and whose length varies from 1 to 30 carbon atoms.
The Mexican MX 297,297 and U.S. Pat. No. 8,722,588 patents, makes mention of supramolecular complexes resulting from alpha olefin sulfonates of sodium with alkyl amido propyl betaines interactions, can be combined with anionic surfactants, preferably of the type 3-hydroxy-alkyl sulfonate of sodium, with cationic surfactants of the type quaternary salts of alkyl ammonium, preferably of the type chloride or bromide of alkyl trimethyl ammonium, with sequestering of divalent ions, preferably oligomers or copolymers derived from itaconic acid and whose average molecular weight are in the range of 200 to 20,000 Daltons, with gels derived from polymers or copolymers selected from of the polyacrylamides group, partially hydrolyzed polyacrylamide, xanthan gum, poly (itaconic acid), poly (acrylic acid), poly (itaconic-co-acrylic-acid acid), poly (itaconates) and poly (acrylates). Also, in said patent it is indicated that the foaming compositions with enhanced stability possess applications in enhanced recovery process and/or production assurance. The patent makes no mention that the compositions have application as wettability modifiers, corrosion inhibitors or antiscale; or that are present in the same copolymers derived from itaconic acid/vinyl sodium sulfonate and/or terpolymers derived from itaconic acid/sodium vinyl sulfonate/aconitic acid.
The Mexican patent application MX/a/2012/014187 (Composición espumante con propiedades modificadoras de la mojabilidad e inhibitorias de la corrosión para alta temperatura y ultra alta salinidad) is related to the collection and use of foaming compositions with modifying-wettability and corrosion-inhibitory properties that controlling the channeling of fluids in naturally fractured carbonate reservoirs, alter the rock wettability favorably in processes for enhanced crude oil recovery and control uniform corrosion problems that occur in production rigs under high temperature and ultra-high salinity conditions; by the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with alkyl hydroxysulfonates of sodium and alkenyl sulphonates of sodium (FIG. 43). The foaming compositions with wettability modifying and corrosion inhibitory properties are characterized for being tolerant to high concentrations of divalent ions such as calcium, magnesium, strontium and barium and that for his application to the reservoir can be used as transport media sea water and/or congenital water characteristic of the reservoir. The patent application does not mention that the compositions have antiscale properties; or that, in the same are present cationic surfactants of the quaternary salts type of alkyl ammonium and/or copolymers derived from itaconic acid/sodium vinyl sulfonate and/or terpolymers derivatives of itaconic acid/sodium vinyl sulfonate/aconitic acid.
In the US patent application US 2007/0142235 A1 (Process for oil recovery using surfactant gels) a composition and process for recovering hydrocarbons are protected, this consist in inject an aqueous solution into a formation that containing hydrocarbon through one or more injection wells, displacing the solution into the formation and recovering the hydrocarbon through one or more producer wells. The aqueous solution contains one or more amphoteric surfactants of alkyl amido betaines type [structure (4)] to form a viscoelastic surfactant gel that can be reduce the interfacial tension and increase the viscosity of the injection fluid simultaneously in some oils and brine. The viscoelastic gels are tolerant to electrolytes and multivalent cations and are particularly useful into reservoirs that have of medium to high temperature, high salinity, high concentrations of divalent ions and low porosity. Inside of the application are mentioned that the composition for recovering hydrocarbons containing one or more amphoteric surfactants selected for their ability to low the interfacial tension and increase the viscosity simultaneously, in an aqueous medium, a secondary surfactant and optionally one or more polymers to provide viscosity residual. This patent application indicates that the secondary surfactant can be selected from the anionic, cationic or nonionic group and that the polymer that provides the residual viscosity is selected from the group polyacrylamide, partially hydrolyzed polyacrylamide, xanthan gum, hydroxyethyl cellulose or guar gum. Also, the patent application mentions that the combination of alkyl amido betaines with secondary surfactants of the linear type dodecyl benzene sodium sulfonatesulfonate and arylalkyl xylene sodium sulfonate reduces the interfacial tension and increases the viscosity of the system. The patent application does not mention that amphoteric surfactants are used based alkyl amido betaines and their mixtures for the foams generation, also it does not indicate that use mixtures of alkyl amido betaines and cationic surfactants of type quaternary salts of alkyl ammonium and/or copolymers derived from the itaconic acid/vinyl sodium sulfonate and/or terpolymers derived from itaconic acid/sodium vinyl sulphonate/aconitic acid.

None of the aforementioned references it claims the development and use of multifunctional foaming compositions obtained from the combination of supramolecular complexes resulting from the interactions of alkyl amido propyl hydroxysultaines and/or alkyl amido propyl betaines and/or alkyl hydroxysultaines and/or alkyl betaines and anionic surfactants of type alkyl hydroxy sulphonates of sodium and/or alkenyl sulphonates of sodium, with cationic surfactants of the type halide of tetra-alkyl ammonium and copolymers derived from itaconic acid/vinyl sodium sulfonate and/or terpolymers derivatives of itaconic acid/sodium vinyl sulfonate/aconitic acid. Such multifunctional compositions are characterized by having high stability in environments of high temperature, high pressure and tolerance to high concentrations of divalent ions like calcium, magnesium, strontium and barium. It is therefore the object of the present invention to provide multifunctional foaming compositions with modifying wettability, uniform and localized corrosion inhibitory and inhibition/dispersion of mineral scales such as calcium carbonate and sulfates of calcium, barium and strontium; composed of supramolecular complexes resulting from interactions of alkyl amido propyl hydroxysultaines and/or alkyl amido propyl betaines and/or alkyl hydroxysultaines and/or alkyl betaines and anionic surfactants of type alkyl hydroxy sulphonates of sodium and alkenyl sulphonates of sodium, with cationic surfactants as tetra-alkyl ammonium halides and copolymers derived from itaconic acid/sodium vinyl sulfonate and/or terpolymers derived from itaconic acid/sodium vinyl sulphonate/aconitic acid. The present invention has the advantage that the generated compositions are multifunctional, control gas channeling in naturally fractured carbonate reservoirs under ultra-high salinity environments, high temperature and a high concentration of divalent ions; control scales problems of mineral salt that occur when the injection and formation water are combined that are incompatible; changing the rock wettability favorably in enhanced crude-oil recovery processes and control uniform corrosion problems in the production rig.